WO2019051857A1 - 一种改性聚氨脂的配方及制备工艺 - Google Patents

一种改性聚氨脂的配方及制备工艺 Download PDF

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WO2019051857A1
WO2019051857A1 PCT/CN2017/102379 CN2017102379W WO2019051857A1 WO 2019051857 A1 WO2019051857 A1 WO 2019051857A1 CN 2017102379 W CN2017102379 W CN 2017102379W WO 2019051857 A1 WO2019051857 A1 WO 2019051857A1
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parts
formulation
modified polyurethane
natural rubber
toluene
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French (fr)
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杨磊
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杨磊
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/14—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves
    • A63B71/141—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves in the form of gloves
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the invention relates to the technical field of polyurethane production, in particular to a formula and a preparation process of a modified polyurethane.
  • Polyurethane material is the abbreviation of polyurethane, the English name is polyurethane, which is a polymer material.
  • Polyurethane is an emerging organic polymer material, which is known as the “fifth largest plastic” and is widely used in many fields of the national economy due to its excellent performance.
  • the application fields of the products include light industry, chemical industry, electronics, textile, medical, construction, building materials, automobile, national defense, aerospace, aviation, etc.
  • Polyurethane slurry is used as a coating to prepare polyurethane synthetic leather and artificial leather.
  • Polyurethane synthetic leather has soft and natural luster, soft handfeel and strong leathery appearance.
  • the present invention provides a modified polyurethane resin formulation and preparation process, and the finished product has a high friction coefficient, which can be well applied to the manufacture of gloves, so that the produced gloves can be used. With greater friction, it is easier to grasp the object and improve the practical effect of the glove. It is worth promoting.
  • a modified polyurethane formulation is composed of the following raw materials in parts by weight:
  • the following raw materials are composed by weight:
  • the following raw materials are composed by weight:
  • the following raw materials are composed by weight:
  • a pretreatment method for natural rubber is: mixing a natural rubber raw material with a dibasic anhydride, adding it into a three-necked flask, and dispersing it under magnetic protection with a magnetic stirring to maintain the temperature of the three-necked flask at 300 ° C. -340 ° C.
  • the present invention also designs a process for preparing a modified polyurethane, comprising the following steps:
  • the raw materials are mixed according to the formulation and then ground into a grinder, and the ground powder is taken out into the reaction vessel, and the temperature is maintained at 85 ° C - 95 ° C, and the gas pressure is 3 MPa.
  • the finished product is cut into strips and placed on a HKGM-1 friction coefficient measuring instrument to measure the friction coefficient.
  • the mold maintaining temperature is 230 ° C - 340 ° C
  • the heating rate is 14 ° C / min - 18 ° C / min.
  • the invention disperses the natural rubber by the magnetic stirring method, so that the polyurethane can better Rubber fusion, using the centrifugal washing method to make the washing effect more, improve the friction coefficient of the material, can be better applied to the production of sports gloves, so that the produced gloves can have greater friction when used, and can be better. It is convenient to grasp the object and improve the practical effect of the glove, which is worth promoting.
  • a modified polyurethane formulation consisting of the following materials in parts by weight:
  • the natural rubber raw material is mixed with the dibasic anhydride, added into a three-necked flask, and dispersed under magnetic protection by magnetic stirring to maintain the temperature of the three-necked flask at 300 ° C - 340 ° C;
  • the preparation process comprises the following steps:
  • the raw materials are mixed according to the formulation and then ground into a grinder, and the ground powder is taken out into the reaction vessel, and the temperature is maintained at 85 ° C - 95 ° C, and the gas pressure is 3 MPa.
  • the finished product is cut into strips and placed on a HKGM-1 friction coefficient measuring instrument to measure the friction coefficient.
  • a modified polyurethane formulation consisting of the following materials in parts by weight:
  • the natural rubber raw material is mixed with the dibasic anhydride, added into a three-necked flask, and dispersed under magnetic protection by magnetic stirring to maintain the temperature of the three-necked flask at 300 ° C - 340 ° C;
  • the preparation process comprises the following steps:
  • the raw materials are mixed according to the formulation and then ground into a grinder, and the ground powder is taken out into the reaction vessel, and the temperature is maintained at 85 ° C - 95 ° C, and the gas pressure is 3 MPa.
  • the finished product is cut into strips and placed on a HKGM-1 friction coefficient measuring instrument to measure the friction coefficient.
  • a modified polyurethane formulation consisting of the following materials in parts by weight:
  • the natural rubber raw material is mixed with the dibasic anhydride, added into a three-necked flask, and dispersed under magnetic protection by magnetic stirring to maintain the temperature of the three-necked flask at 300 ° C - 340 ° C;
  • the preparation process comprises the following steps:
  • the raw materials are mixed according to the formulation and then ground into a grinder, and the ground powder is taken out into the reaction vessel, and the temperature is maintained at 85 ° C - 95 ° C, and the gas pressure is 3 MPa.
  • the finished product is cut into strips and placed on a HKGM-1 friction coefficient measuring instrument to measure the friction coefficient.
  • the invention has the advantages that the natural rubber is dispersed by the magnetic stirring method, so that the polyurethane can be better fused with the rubber, and the centrifugal washing method is used to make the washing effect more, and the friction coefficient of the material is improved. It can be better applied to the production of sports gloves, so that the produced gloves can have greater friction when used, which can better grasp the objects and improve the practical effect of the gloves, which is worth promoting.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种改性聚氨脂的配方，按照重量份数由如下原料组成：天然橡胶90-100份，丙酮100-110份，甲苯80-90份，聚酯多元醇70-90份，丁二醇40-50份，二氧化硅30-40份，甲苯二异氰酸酯20-30份，催化剂6-8份，防老剂4-6份。

Description

一种改性聚氨脂的配方及制备工艺 技术领域
本发明涉及聚氨脂生产技术领域，具体涉及一种改性聚氨脂的配方及制备工艺。
背景技术
聚氨酯材料是聚氨基甲酸酯的简称，英文名称是polyurethane，它是一种高分子材料。聚氨酯是一种新兴的有机高分子材料，被誉为“第五大塑料”，因其卓越的性能而被广泛应用于国民经济众多领域。产品应用领域涉及轻工、化工、电子、纺织、医疗、建筑、建材、汽车、国防、航天、航空等，聚氨酯浆料用作涂层制备聚氨酯合成革、人造革。聚氨酯合成革具有光泽柔和、自然，手感柔软，真皮感强的外观，具有与基材粘接性能优异、抗磨损、耐挠曲、抗老化、抗霉菌性好等优异的机械性能，同时还具备耐寒性好、透气、可洗涤、加工方便、价格优廉等优点，是天然皮革的最为理想的替代品，广泛应用于服装、制鞋、箱包、家具、体育等行业。随着社会的发展，越来越多的手套采用了聚氨脂来制造，现在有很多的手套应用于运动，在运动时需要提供较大的摩擦力，很多的聚氨脂材料都无法满足这个要求。
发明内容
针对以上问题，本发明提供了一种改性聚氨脂的配方及制备工艺，生产出的成品具有很高的摩擦系数，可以很好的应用于手套的制造，使得生产出的手套使用时能拥有更大的摩擦力，能更好的方便抓住物体，提高了手套的实用效果，值得推广。
为了实现上述目的，本发明采用的技术方案如下：一种改性聚氨脂的配方，按照重量份数由如下原料组成：
天然橡胶90-100份，丙酮100-110份，甲苯80-90份，聚酯多元醇70-90份，丁二醇40-50份，二氧化硅30-40份，甲苯二异氰酸酯20-30份，催化剂6-8份，防老剂4-6份。
作为本发明一种优选的技术方案，按照重量份数由如下原料组成：
天然橡胶90份，丙酮100份，甲苯80份，聚酯多元醇70份，丁二醇40份，二氧化硅30份，甲苯二异氰酸酯20份，催化剂6份，防老剂4份。
作为本发明一种优选的技术方案，按照重量份数由如下原料组成：
天然橡胶95份，丙酮105份，甲苯85份，聚酯多元醇75份，丁二醇45份，二氧化硅35份，甲苯二异氰酸酯25份，催化剂7份，防老剂5份。
作为本发明一种优选的技术方案，按照重量份数由如下原料组成：
天然橡胶100份，丙酮110份，甲苯90份，聚酯多元醇90份，丁二醇50份，二氧化硅40份，甲苯二异氰酸酯30份，催化剂8份，防老剂6份。
作为本发明一种优选的技术方案，对于天然橡胶的预处理方法：将天然橡胶原料混合二元酐，加入三口烧瓶内，在氮气的保护下，采用磁力搅拌分散，保持三口烧瓶温度为300℃-340℃。
另外本发明还设计了一种改性聚氨脂的制备工艺，包括如下步骤：
(1)将原料按配方混合后加入研磨机内研磨，将研磨好的粉末取出加入反应釜内，保持温度为85℃-95℃，气压为3MPa。
(2)将反应釜内的溶液取出，在油浴锅加热至70℃-80℃，加热4h-5h后取出降温。
(3)降温之后，混合适量乙醇后加入离心机离心洗涤，洗涤30min后加入真空干燥箱内进行真空干燥处理。
(4)干燥处理之后放在双辊开炼机上，经过硫化处理后加入模具内成型。
(5)将成品切割成条状，放置在HKGM-1摩擦系数测量仪上，进行摩擦系数的测量。
作为本发明一种优选的技术方案，所述步骤(4)中，模具保持温度为230℃-340℃，加热速率为14℃/min-18℃/min。
本发明的有益效果：
本发明通过磁力搅拌方法，将天然橡胶分散，使得聚氨脂能更好的与 橡胶融合，利用离心洗涤的方法使得洗涤效果更加，提高了材料的摩擦系数，能更好的应用于运动手套的生产制造，使得生产出的手套使用时能拥有更大的摩擦力，能更好的方便抓住物体，提高了手套的实用效果，值得推广。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合几个具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1：
一种改性聚氨脂的配方，按照重量份数由如下原料组成：
天然橡胶90份，丙酮100份，甲苯80份，聚酯多元醇70份，丁二醇40份，二氧化硅30份，甲苯二异氰酸酯20份，催化剂6份，防老剂4份。
对于天然橡胶的预处理方法：将天然橡胶原料混合二元酐，加入三口烧瓶内，在氮气的保护下，采用磁力搅拌分散，保持三口烧瓶温度为300℃-340℃；
其制备工艺包括如下步骤：
(1)将原料按配方混合后加入研磨机内研磨，将研磨好的粉末取出加入反应釜内，保持温度为85℃-95℃，气压为3MPa。
(2)将反应釜内的溶液取出，在油浴锅加热至70℃-80℃，加热4h-5h后取出降温。
(3)降温之后，混合适量乙醇后加入离心机离心洗涤，洗涤30min后加入真空干燥箱内进行真空干燥处理。
(4)干燥处理之后放在双辊开炼机上，经过硫化处理后加入模具内成型。
(5)将成品切割成条状，放置在HKGM-1摩擦系数测量仪上，进行摩擦系数的测量。
实施例2：
一种改性聚氨脂的配方，按照重量份数由如下原料组成：
天然橡胶95份，丙酮105份，甲苯85份，聚酯多元醇75份，丁二醇45份，二氧化硅35份，甲苯二异氰酸酯25份，催化剂7份，防老剂5份。
对于天然橡胶的预处理方法：将天然橡胶原料混合二元酐，加入三口烧瓶内，在氮气的保护下，采用磁力搅拌分散，保持三口烧瓶温度为300℃-340℃；
其制备工艺包括如下步骤：
(1)将原料按配方混合后加入研磨机内研磨，将研磨好的粉末取出加入反应釜内，保持温度为85℃-95℃，气压为3MPa。
(2)将反应釜内的溶液取出，在油浴锅加热至70℃-80℃，加热4h-5h后取出降温。
(3)降温之后，混合适量乙醇后加入离心机离心洗涤，洗涤30min后加入真空干燥箱内进行真空干燥处理。
(4)干燥处理之后放在双辊开炼机上，经过硫化处理后加入模具内成型。
(5)将成品切割成条状，放置在HKGM-1摩擦系数测量仪上，进行摩擦系数的测量。
实施例3：
一种改性聚氨脂的配方，按照重量份数由如下原料组成：
天然橡胶100份，丙酮110份，甲苯90份，聚酯多元醇90份，丁二醇50份，二氧化硅40份，甲苯二异氰酸酯30份，催化剂8份，防老剂6份。
对于天然橡胶的预处理方法：将天然橡胶原料混合二元酐，加入三口烧瓶内，在氮气的保护下，采用磁力搅拌分散，保持三口烧瓶温度为300℃-340℃；
其制备工艺包括如下步骤：
(1)将原料按配方混合后加入研磨机内研磨，将研磨好的粉末取出加入反应釜内，保持温度为85℃-95℃，气压为3MPa。
(2)将反应釜内的溶液取出，在油浴锅加热至70℃-80℃，加热4h-5h 后取出降温。
(3)降温之后，混合适量乙醇后加入离心机离心洗涤，洗涤30min后加入真空干燥箱内进行真空干燥处理。
(4)干燥处理之后放在双辊开炼机上，经过硫化处理后加入模具内成型。
(5)将成品切割成条状，放置在HKGM-1摩擦系数测量仪上，进行摩擦系数的测量。
样品号 标准件 实施例1 实施例2 实施例3
摩擦系数 0.75 0.86 0.89 0.84
由上表可知，实施例1至实施例3所得成品的摩擦系数都优于标准品，性能优于标准品。
基于上述，本发明的优点在于，本发明通过磁力搅拌方法，将天然橡胶分散，使得聚氨脂能更好的与橡胶融合，利用离心洗涤的方法使得洗涤效果更加，提高了材料的摩擦系数，能更好的应用于运动手套的生产制造，使得生产出的手套使用时能拥有更大的摩擦力，能更好的方便抓住物体，提高了手套的实用效果，值得推广。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种改性聚氨脂的配方，其特征在于，按照重量份数由如下原料组成：
    天然橡胶90-100份，丙酮100-110份，甲苯80-90份，聚酯多元醇70-90份，丁二醇40-50份，二氧化硅30-40份，甲苯二异氰酸酯20-30份，催化剂6-8份，防老剂4-6份。
  2. 根据权利要求1所述的一种改性聚氨脂的配方，其特征在于，按照重量份数由如下原料组成：
    天然橡胶90份，丙酮100份，甲苯80份，聚酯多元醇70份，丁二醇40份，二氧化硅30份，甲苯二异氰酸酯20份，催化剂6份，防老剂4份。
  3. 根据权利要求1所述的一种改性聚氨脂的配方，其特征在于，按照重量份数由如下原料组成：
    天然橡胶95份，丙酮105份，甲苯85份，聚酯多元醇75份，丁二醇45份，二氧化硅35份，甲苯二异氰酸酯25份，催化剂7份，防老剂5份。
  4. 根据权利要求1所述的一种改性聚氨脂的配方，其特征在于，按照重量份数由如下原料组成：
    天然橡胶100份，丙酮110份，甲苯90份，聚酯多元醇90份，丁二醇50份，二氧化硅40份，甲苯二异氰酸酯30份，催化剂8份，防老剂6份。
  5. 根据权利要求1所述的一种改性聚氨脂的配方，其特征在于，对于天然橡胶的预处理方法：将天然橡胶原料混合二元酐，加入三口烧瓶内，在氮气的保护下，采用磁力搅拌分散，保持三口烧瓶温度为300℃-340℃。
  6. 一种改性聚氨脂的制备工艺，其特征在于，包括如下步骤：
    (1)将原料按配方混合后加入研磨机内研磨，将研磨好的粉末取出加入反应釜内，保持温度为85℃-95℃，气压为3MPa。
    (2)将反应釜内的溶液取出，在油浴锅加热至70℃-80℃，加热4h-5h后取出降温。
    (3)降温之后，混合适量乙醇后加入离心机离心洗涤，洗涤30min后加入真空干燥箱内进行真空干燥处理。
    (4)干燥处理之后放在双辊开炼机上，经过硫化处理后加入模具内成型。
    (5)将成品切割成条状，放置在HKGM-1摩擦系数测量仪上，进行摩擦系数的测量。
  7. 根据权利要求1所述的一种改性聚氨脂的制备工艺，其特征在于，所述步骤(4)中，模具保持温度为230℃-340℃，加热速率为14℃/min-18℃/min。
PCT/CN2017/102379 2017-09-13 2017-09-20 一种改性聚氨脂的配方及制备工艺 WO2019051857A1 (zh)

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